The photoluminescence and electroluminescence of poly(9-vinylcarbazole) (PVCz) containing different ratio 1.3,5-dimethly-3,5-di-tert-butyl-4,4-diphenoquinone (MBDQ), 1.3,5-diemthyl-3.5-di-tert-butyl-4,4-stylbenquinone (MBSQ) were characterized. As the contents of DQ and SQ increased, the intensity of peaks at 516 and 540nm increased in PL spectra. The results of TOF measurement were shown that the hole mobility of PVCz decreased as the ratio of DQ or SQ increased. On the other hand, the electron mobility of PVCz increased. Therefore Electron transport is more favorable than hole transport in these charge transfer complexes, due to the stronger localization of the holes. Evidence for better electron transport is the higher mobility of electrons in pure DQ or SQ compared to hole mobility in pure PVCz, and lower DQ or SQ concentration required for equivalent mobilities in the charge-transfer complexes.